



Ae 
ORATORY MANUAL 


OF 


ORGANIC CHEMISTRY 


W. R. ORNDORFF 








De C.«HEATH & CO. 


BOSTON NEW YORK CHICAGO 





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RESEARCH LIBRARY 
THE GETTY RESEARCH INSTITUTE 


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A 


LABORATORY MANUAL 


CONTAINING 
DIRECTIONS FOR A COURSE OF EXPERIMENTS 


IN ORGANIC CHEMISTRY 


SYSTEMATICALLY ARRANGED TO ACCOMPANY 


REMSEN’S ORGANIC CHEMISTRY 
FIFTH REVISION 


BY 


W. R. ORNDORFF, A.B., Pu.D. 


PRoressoR of ORGANIO CHEMISTRY IN CORNELL UNIVERSITY 


Peete ait. & CO, PUBLISHERS 
BOSTON NEW YORK CHICAGO 





By W. R. ORNDORFF. — 








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PREFACE. 


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At the author’s request I have carefully examined 
this Manual; and, as a result, I have recommended its 
publication, in the belief that it will be a valuable 
adjunct to my “Introduction to the Study of the 
Compounds of Carbon.” Great care has evidently 
been taken to determine the best conditions for each 
experiment; and, in many cases, the directions given 
are undoubtedly better than those given in my book. 
This is largely due to the fact that the author has, 
for a number of years, had charge of the work of 
preparation of compounds of carbon in a large labora- 
tory; and he has therefore had an excellent oppor- 
tunity thoroughly to test different methods, — an 
opportunity which he has well utilized. 


IRA REMSEN. 
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EXPERIMENT. 1. 
FRACTIONAL DISTILLATION. 


1. 


Fit up an apparatus like the one shown in Fig. 1 
(text-book, page 5), using a l-liter distilling-flask 
(Fig. 2, text-book), in place of the flask and thermome- 
ter tube. Add 300 c.c. of alcohol and 300 c.c. of 
water to the flask, and separate the two by fractional 
distillation, following closely the directions given on 
pages 6 and 7 of the text-book. Distil slowly and 
regularly, using an ebullator-tube. Measure each 
fraction, and the residue left in the flask at the end 
of each series of distillations. Fill in the blanks in the 
following table, and draw your own conclusions 
from the results. 


DISTILLATIONS. | 
FRACTIONS. 


SS | — —— ) | | |] 


78°- 83° 
83°— 88° 
88°9-— 938° 
93°— 98° 
98°-100° 
Residues 
Totals 


For further information regarding all kinds of dis- 
tillation, and for the methods of determining boiling- 
points, the student is referred to Lassar-Cohn’s very 
valuable book, A Laboratory Manual of Organic 
Chemistry, translated by Alexander Smith (Mac- 





millan & Co., 1895), and to Sydney Young’s book 
on Fractional Distillation (Macmillan & Co., 1903). 


EXPERIMENT 1. 


FRACTIONAL DISTILLATION. 


2. 


Use a 1-liter round-bottom flask, an ebullator-tube,! 
and a Hempel or Vigreux distilling-tube. Run only 
two series of distillations, using 300 c.c. of water and 
300 c.c. of alcohol, and follow the directions given in 
the text-book. If time permits compare the results 
obtained with a simple distilling-flask with those 
made with the distilling-tube. 

1See Mulliken, ‘‘Identification of Organic Compounds,”’ page 223. 


EHXPERIMENT 2. 


DETERMINATION OF MELTING-POINTS. 


il. 


Determine the melting-points of the substances 
given below, proceeding as directed in the text-book, 
page 9, using, however, the 
apparatus here figured: A 
is a pear-shaped flask, of 
100 c.c. capacity, ? filled 
with colorless concentrated 
sulphuric acid. The ther- 
mometer is held in place 
by a cork with a groove 
cut through to the ther- 
mometer, so that the scale 
of the thermometer may 
be read. The capillary 
tube is fastened to the 
thermometer by a rubber 





band, or, better, by a 
small piece of platinum 
wire, so that the substance and the bulb of the ther- 
mometer are side by.side. By fastening two capillary 
tubes, one on each side of the thermometer, two deter- 
minations may be made at once. Should the sulphuric 
acid become dark colored (from the organic matter 
suspended in it), it may be rendered colorless by 





removing the thermometer, adding a small quantity 
of concentrated nitric acid, and heating until the nitric 
acid has been driven off. (Hood.) For further details 
concerning melting-point determinations, see Lassar- 
Cohn’s book, page 68. 


MELTING-POINTS. 


SUBSTANCES. 
Observed. Given in Text. 


Naphthalene. 
Urea. 

Succinic acid. 
Anthracene. 
Anthraquinone. 


EXPERIMENT 2. 
DETERMINATION OF MELTING-POINTS. 
2. 


Use the Thiele apparatus for determining melting- 
points (see Fig. 4 on page 10 of the text-book) and 
follow closely the directions given in the text-book. 





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EXPERIMENT 3. 
MARSH GAS. 


Grind together intimately 20 grams of fused sodium 
acetate and 40 grams of powdered soda-lime. Heat 
the mixture-in a 500 c.c. balloon flask with a triple 
burner. Collect the gas evolved over water in wide- 
mouthed cylinders of 200 c.c. capacity. What is left 
in the retort? Prove it. Write out the reaction. 

Determine the properties of the gas, including 
color, odor, specific gravity (lighter or heavier than 
air), inflammability, solubility, etc. Mix one volume 
of marsh gas and two volumes of oxygen and ex- 
plode by applying a lighted taper. Why are the gases 
mixed in this proportion? What are the products 
of the explosion ? 


CaAuTIon. — In working with gases see that all joints 
of the apparatus are tight before beginning the expert- 


ment. 





EXPERIMENT 4. 
CHLOROFORM. 


275 grams of bleaching-powder and 800 c.c. of 
water are put into a 3-liter balloon-flask, and thor- 
oughly mixed. The flask is closed with a 3-hole 
stopper. Through one hole passes a separating funnel, 
reaching to the bottom of the flask; through the 
second, a tube bent at right angles, and also reaching 
to the bottom of the flask; and through the third, the 
exit tube. Connect the flask with the condenser and 
receiver, heat on a water-bath, and add very gradually, 
through the separating funnel, a mixture of 22 grams 
of acetone and 70 c.c. of water, shaking the flask con- 
stantly during the addition of the acetone and water. 
After all the acetone has been added and the reaction 
is completed, steam is passed in through the tube 
reaching to the bottom of the flask, and the distillation 
in steam is continued as long as chloroform distils with 
the water. 

Separate the chloroform from the water by means 
of a separating funnel; wash it with dilute caustic 
soda solution (?), and then with water (?). Remove 
the water completely, add calcium chloride to remove 
the last traces of water, pour off the chloroform from 
the calcium chloride and distil the chloroform, noting 
the boiling-point. 

Save a specimen of the chloroform, and determine 
its properties, — color, odor, taste, boiling-point, 


EXPERIMENT 5.1 
IODOFORM. 


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Dissolve 15 grams of potassium carbonate in 100 
c.c. of water, filter the solution if necessary, and 
add 16 grams of alcohol (94%). The flask contain- 
ing the solution is warmed to 70°C, and 20 grams of 
iodine are then gradually added, with constant shaking 
of the flask. A gas is given off; what is it? Filter 
off the iodoform, wash with water, dry in the air on 
filter-paper, and recrystallize from alcohol. Deter- 
mine its melting-point, solubility in water, alcohol, 
ether, carbon bisulphide; crystal form, taste, odor, 
and color. The filtrate from the iodoform is evap- 
orated to crystallization and the crystals examined. 
What are they? Prove it. 

Save a specimen of the crystallized iodoform and 
the potassium iodide. 

Reactions are to be written out after chloral has 
been considered. 


1 Make iodoform by either of the two methods here given. The 
second has given the better results in this laboratory. 





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EXPERIMENT 5. 
IODOFORM. 


2. 


Dissolve 10 grams of potassium iodide in 500 
c.c. of water and add 2 grams of acetone. To this 
mixture add, through a dropping-funnel or burette, 
with constant shaking, a dilute solution of sodium 
hypochlorite as long as a precipitate is formed. Allow 
the precipitate to settle, decant off the liquid, wash 
with water two or three times, filter, drain thor- 
oughly, dry on filter-paper, and recrystallize from 
alcohol. Does any iodide remain in solution? De. 
termine the melting-point, solubility in water, alco. 
hol, ether, carbon bisulphide, etc.; crystal form, 
taste, odor, and color. 

Save a specimen of the crystallized iodoform. Write 
out the reactions after chloral and acetone have been 
considered. 

The solution of sodium hypochlorite used in this 
experiment may be readily made by precipitating © 
all the calcium in a solution of bleaching-powder 
(chloride of lime) with a solution of sodium carbo- 
nate. <A slight excess of sodium carbonate will not 
interfere with the reaction. 





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EXPERIMENT 6.1 


ETHYL BROMIDE. 
(Hoop.) 
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10 grams of dry (?) amorphous phosphorus and 6 — 
grams of absolute (?) alcohol are brought together 
in a 500 c.c. round-bottomed flask which is kept cold 
by ice-water; 60 grams (19 c.c.) of bromine are then 
gradually added through a separating-funnel, drop 
by drop, with constant shaking of the flask. After 
all the bromine has been added, the flask is connected 
with a return condenser (see Fig. 8, page 71, text- 
book) and gently heated on a water-bath until the 
reaction is completed. ‘The condenser is then turned 
down, and the ethyl bromide distilled off. Wash this 
with dilute caustic soda solution (?), then with 
water; drain off the water, and dry by warming 
slightly with fused calcium chloride, using a return 
condenser (?). Pour off from the calcium chloride 
into a dry distilling-flask and distil, noting the 
boiling-point. 

Determine color, odor, taste, specific gravity 
(heavier or lighter than water), inflammability 
(Hood). Save specimen of the pure product. What 

1 Hither of the two methods given may be used’ to prepare 


ethyl bromide; the second has given better results in this 
laboratory. 





EXPERIMENT 6. 


ETHYL BROMIDE. 
(Hoop.) 


2. 


100 grams of finely powdered potassium bromide 
are placed in a 250 c.c. distilling-flask, and a cooled 
mixture of 42 grams of absolute alcohol (95% will 
do) and 100 grams of concentrated sulphuric acid is 
slowly added. ‘The flask is then connected with the 
condenser and heated on a sand-bath until all the 
ethyl bromide has been distilled. The ethyl bromide 
is then separated from the water, washed first with 
dilute caustic soda solution, then with water, and 
dried by warming not over 35° (?) on a water-bath with 
fused calcium chloride (using a return condenser — 
see Fig. 8, page 71, text-book). The product is then 
distilled, carefully noting the boiling-point. Save a 
specimen of the pure ethyl bromide. 

Determine its physical properties: color, taste, 
odor, specific gravity (lighter or heavier than 
water), inflammability (Hood), boiling-point, etc. 
Determine the action of silver nitrate solution at 
boiling heat on ethyl bromide. What remains in the 
flask in which the ethyl bromide was made? Prove 
it. Write out all reactions. 


1Use an adapter, and surround the receiver with a freezing 
mixture as in Experiment 10 (?). 


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EXPERIMENT 7. 
FERMENTATION OF GLUCOSE. 


Dissolve 150 grams of glucose in about 14 liters of 
water, add 60 c.c. of a solution of Pasteur salts. 
Put the mixture into a 2-liter flask, add + cake of 
compressed yeast (cut fine), and warm to 25° C. on a 
water-bath. Connect the flask with a cylinder con- 
taining limewater (protected from the air by a layer 
of kerosene or benzene). Keep the temperature as 
near 25° as possible (by warming on a water-bath), 
until fermentation ceases; then allow the yeast to 
settle, and draw off the clear liquid. Distil 500 c.c. of 
this, using a Hempel or Vigreux distilling-tube (?), 
test the first 5 c.c. of the distillate to see if it burns, and 
test the remainder for alcohol (see Mulliken — Iden- 
tification of Organic Compounds, page 166). Save a 
specimen and write out all reactions. 

Explain why Pasteur salts are used and why the 
limewater must be protected. from the air. What 
gas comes off? Will the alcohol burn? Try it. 

For further information on the subject of fermen- 
tation the student is referred to Schutzenberger’s 


book on Fermentation. 


1The formula for Pasteur salts, based on an analysis of the 
inorganic constituents of the yeast plant, is as follows : — 


Potassium phosphate : , ‘ ; 2.00 pts. 
Calcium a E f : . ¥ 0,20; 
Magnesium sulphate : i $ ~« 0.20% 
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EXPERIMENT 8. 
ABSOLUTE ALCOHOL. 


Heat, on the water-bath, 1 liter of alcohol (95 %) 
with 500 grams. of quicklime, broken into small 
lumps (not powder), in a 8-liter short-necked balloon 
flask provided with a return condenser (see text- 
book, page 71, Fig. 8). After boiling ,the alcohol with 
the lime for six hours, distil off the alcohol the next 
day, and determine whether it is free from water (see 
Roscoe and Schorlemmer’s Treatise on Chemistry, 
Vol. III. Part I. page 298; and Beilstein’s ‘‘Organ- 
ische Chemie,” 3d edition, Vol. I. page 222). If not, 
repeat the process with the distillate. 

Save a specimen of the pure alcohol. Explain 
the process, and determine the specific gravity of 
the alcohol and the per cent of water it contains. 

Determine the properties of pure alcohol, includ- 
ing color, odor, taste, boiling-point, inflammability. 
Does its vapor mixed with air explode? Try it, 
Does it solidify when cooled? What use is made 
of this fact? Is alcohol a good solvent? ‘Try it. 

The student is recommended to read the chapter 
on alcoholometry and the methods of determining 
the amount of alcohol in wines, beer, etc., in Roscoe 
and Schorlemmer’s Treatise on Chemistry, Vol. III. 
Part I. page 301. 


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EXPERIMENT 9. 
CALCIUM ETHYL SULPHATE. 


Add 50 grams of concentrated sulphuric acid 
to 70 grams of alcohol without cooling, and heat 
the mixture on the water or steam bath for a 
quarter of an hour. After the mixture is cold, pour 
it slowly, and with constant stirring, into a porcelain 
dish containing crushed ice or snow (?). Then 
dilute with ice-water to about a liter and a half. The 
acid is now nearly neutralized by adding slaked lime 
or precipitated chalk, ice being added from time to 
time to prevent any rise of temperature (?). The 
solution is then filtered off from the calcium sulphate 
through a muslin filter stretched on a wooden frame, 
or, better, by the method of reverse filtration. The 
apparatus for this latter process consists of a small 
funnel which is covered with white cotton cloth, and 
which is connected by a rubber tube with a bottle, 
the bottle in turn being connected with a suction- 
pump. The funnel is placed in the mixture to be 
filtered, and the pump started. The liquid is drawn 
through the funnel into the bottle, and is quickly 
and completely filtered. The precipitate is then 
treated with 3 liter of cold water and the liquid again 
filtered off. Clear limewater is now added to the 
combined filtrates to alkaline reaction (?), and this 
solution is evaporated to crystallization on the steam 
or water-bath, taking care to filter off the calcium 


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sulphate which separates out as the solution is con- 
centrated. Explain. After the first crop of crystals 
has formed, filter them off, using a Witt plate and a 
filtering-flask connected with a pump, and repeat the 
process with the mother liquor. Drain the crystals 
thoroughly and dry on drying-paper. 

Determine the color, taste, crystal form, solubil- 
ity, etc., of the crystals obtained. Save a specimen. 
Does the salt contain water of crystallization? Try 
it. Does it contain carbon? Prove it. 

Write out all reactions. 





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EXPERIMENT 10. 
ETHER. 


Arrange an apparatus like the one shown in the figure 


below. 





A is a round-bottomed, wide-necked flask of 2 
liters’ capacity. 

B is a cylindrical separating-funnel reaching to 
the bottom of A. 

(, a short thermometer, the bulb of which must 
dip below the surface of the liquid. 

D, an adapter which is connected with the receiver 
by a doubly bored stopper. 

E, a receiver, which must be surrounded with a 
freezing mixture (ice and salt). 

Into the flask A put a cooled mixture of 325 grams 
of concentrated sulphuric acid and 170 grams of 
alcohol (95%). Heat the mixture in the flask A un- 
til the temperature reaches 140° C. Then cautiously 
open the stopcock of the separating-funnel and let a 


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slow stream of alcohol zn the form of vapor bubble 
through the liquid, regulating the flow of alcohol so 
that the temperature of the mixture is kept as nearly 
140° C. as possible (not below 140° and not above 
145°). When 250 grams of alcohol have been run in, 
the operation is stopped. The distillate consists of 
two layers, and contains, besides ether, water, alcohol, 
and sulphurous acid. The watery layer is removed 
by means of a liter separating-funnel, and the ether 
is washed first with dilute caustic soda solution (?), 
then two or three times with small quantities of dis- 
tilled water (?). The washed ether is now treated 
with one-half its weight of fused calcium chloride, 
and distilled on a water-bath through a Hempel or 
Vigreux distilling-tube, taking care that the tempera- 
~ ture does not rise above 50° C. The distillate must be 
kept cold by ice-water. Weigh the ether obtained and 
see how the yield accords with that required by theory. 

Determine the boiling-point, specific gravity, color, 
solubility in alcohol and water, taste, and odor. 
Place a few drops on the hand and note the effect 
produced. Mix a lttle in a wide, strong cylinder 
with air, and apply a lighted taper. Explain. Is it 
a good solvent? Try it. Does water dissolve ether? 
Does ether dissolve water? 

Write out all reactions. Save a specimen of ether. 


CAUTION. — ln working with ether always avoid the 
neighborhood of flames (?). 





EXPERIMENT 11. 


Put a few cubic centimeters of ether into a small 
evaporating-dish and put the dish on a sand-bath. 
Apply a flame. Note the result. 

What are the products of the combustion? Prove it. 


EXPERIMENT 12. 


Into a thin glass test-tube put 5 or 10 c.c. of water 
and place the tube in a small beaker containing 
some ether. Through a glass tube, just reaching to 
the surface of the ether, pass air from a foot bellows 
or a blast. In afew moments the water in the test- 
tube will be frozen. Explain. 


EXPERIMENT 18. 
ALDEHYDE. 


Dissolve 5 grams of potassium bichromate in water 
and add gradually 15 c.c. of concentrated sulphuric 
acid. Is there any change of color? What is formed? 
Now add a few cubic centimeters of alcohol and warm 
the tube. Notice the odor. What is formed? Does 
the solution change color? Explain. What has 
become of the potassium bichromate and the alcohol ? 
What is left in the solution? Prove it and write out 
all reactions. 





EXPERIMENT 14. 
ALDEHYDE. 


225 grams of potassium bichromate (in small pieces 
not powdered) are placed in a 8-liter round-bottomed 
flask, and the flask surrounded with a freezing mix- 
ture. Then add through a separating-funnel a cool 
mixture of 120 grams of alcohol (95%), 900 c.c. of | 
water, and 300 grams of concentrated sulphuric acid, 
shaking the flask during the addition of the mixture, 
so as to avoid any great rise of temperature. The 
flask is then removed from the freezing mixture, con- 
nected with a Hempel or Vigreux distilling-tube (40 
to 50 c.m. long), a condenser, and receiver, the latter 
surrounded with a freezing mixture. After the mixture 
has been gradually warmed up to the temperature of 
the air by heating on the water-bath, heat the flask 
gently with direct flame and collect the distillate, taking 
care that the temperature shown by the thermometer 
in the Hempel or Vigreux tube does not exceed 95° C. — 
Distil twice over calcium chloride. Collect up to 70° 
in the first redistillation and up to 30° in the second. 

Determine the taste, odor, color, boiling-point, solu- 
bility, etc., of the aldehyde obtained. Is it lighter or 
heavier than water? Does it dissolve iodine, sulphur, 
phosphorus? ‘Try it. Heat a few drops of aldehyde 
with caustic potash solution. Note change of color 
and odor (characteristic of aldehyde). Save a few 
drops for Experiment 15. 


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Cool 10 c.c. of this aldehyde in a small flask in a 
freezing mixture and pass in a few bubbles of hydro- 
chloric acid gas.1 What takes place? Explain. Fil- 
ter off the crystals, wash them with alcohol, and cool 
the first filtrate in a mixture of concentrated hydro- 
chloric acid and crushed ice (or ice and crystallized 
calcium chloride). Note result. Explain. To 10 
c.c. of the aldehyde add 20 c.c. of anhydrous ether, 
cool in a freezing mixture, and saturate with dry 
ammonia gas, obtained by heating a concentrated 
solution of aqueous ammonia and passing the gas 
evolved through a cylinder filled with quicklime or 
soda-lime (?). Note result. Explain. Filter off the 
crystals, wash with ether, and dry on drying-paper. 
Let the filtrate evaporate spontaneously in a crystal- 
lizing-dish, when more crystals will be obtained. 

Save specimens of aldehyde, Bevery te paralde- 
hyde, and aldehyde ammonia. 

Write out all reactions. 


1 For the success of this experiment it is essential that the 
aldehyde be dry. Dry it with calcium chloride. 





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EXPERIMENT 15. 
DETECTION OF ALDEHYDE. 


Take 10 c.c. of a solution of silver nitrate, add 
cautiously drop by drop a dilute solution of ammonia 
until the silver oxide first precipitated is just dissolved, 
taking care to avoid any excess of ammonia. An 
ammoniacal solution of silver oxide is thus obtained. 

Clean a test-tube thoroughly by boiling some con- 
centrated nitric acid in it, pouring out the acid and 
washing with distilled water. Heat the ammoniacal 
silver oxide solution to boiling in the cleaned test- 
tube, then add a drop of the aqueous solution of 
the aldehyde obtained in Experiment 14, noting the 
result. Explain. What becomes of the aldehyde? 
What use is made of this method in the arts? 

Test the delicacy of this reaction both for aldehyde 
and for silver. (See in this connection Roscoe and 
Schorlemmer’s Treatise on Chemistry, Vol. III. page 
478.) 

Write out all reactions and save a specimen of the 
silver mirror. 








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EXPERIMENT 16. 
FORMIC ACID. 


Into a 500 c.c. dry distilling-flask put 200 grams of 
erystallized oxalic acid and 200 grams of anhydrous 
glycerin Gf the glycerin is not anhydrous, heat it in 
a porcelain dish under the hood to 175° C. for an hour 
or two). Insert a thermometer through the cork, so 
that the bulb dips below the surface of the glycerin, 
and connect the flask with a condenser and a receiver. 
Heat gently with a burner, keeping the temperature 
of the liquid between 100°-115° C. What gas is given 
off? When this gas ceases to be evolved, and after 
the contents of the flask have cooled to 75°, add 50 
grams more of the crystallized oxalic acid, and heat as 
before. Repeat this addition of oxalic acid until 250 
c.c. of distillate have collected in the receiver. Put 
the glycerin into the bottle marked “ Glycerin Resi- 
dues,” and set aside 25 c.c. of the distillate for the 
experiments given below. Divide the rest into three 
portions. Neutralize one portion with chalk or slaked 
lime, filter, evaporate to crystallization, and save speci- 
men of the calcium salt. Warm the second portion 
with a slight excess of lead carbonate or oxide, decant 
through a filter, and extract the precipitate two or 
three times with boiling water (?). Evaporate the 
combined filtrates to crystallization and save a speci- 
men of the lead salt. Heat the third portion until 
saturated with freshly precipitated copper hydroxide 





(obtained by precipitating a solution of copper sul- 
phate with caustic soda solution and washing the 
precipitate thoroughly with water), filter, evaporate 
the filtrate to crystallization, and save a specimen of 
the copper salt. 

With the 25 c.c. of the distillate perform the fol- 
lowing experiments : — 

(a) Heat a small quantity with some mercuric 
oxide and note the result. Explain. 
(6) Heat some with a solution of silver nitrate 
and describe and explain what takes place. 
(Explain why these two reactions are charac- 
teristic of formic acid.) 

Describe both the physical and chemical properties 
of all the salts made; save specimens of all and of 
the distillate. Write out all reactions. 

(Use the material in the bottle marked “ Glycerin 
Residues” to start with, if it is available, instead 
of glycerin itself, and add only 50 grams of oxalic 
acid at a time.) 


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EXPERIMENT 17. 


ACETIC ACID. 


(Hoop.) 


150 grams of fused sodium acetate are powdered 
and put into a 500 c.c. dry distilling-flask. The flask 
is cooled, and 180 grams of concentrated sulphuric 
acid (sp. gr. 1.842) are gradually added through a 
funnel-tube reaching to the bottom of the flask. The 
flask is then connected with a condenser and receiver 
and heated on a sand-bath. The distillate is sub- 
jected to fractional distillation, using a short Hempel 
distilling-tube, or a distilling-flask,! with a column of 
glass beads in the neck (see figure), or better a short 
Vigreux distilling-tube. 

First an aqueous acid passes over 
and is collected separately, but 
between 117° and 119° the anhy- - 
drous acid distils. Cool this distil- 
late (between 117°-119°) with ice- 
water, and note what takes place. 
Save specimen of the glacial acid. 
Why is the first distillate not anhy- 
drous ? 

A portion of the first distillate of 
the aqueous acid is carefully neu- 





tralized with caustic soda solution 

1 These flasks, which are exceedingly convenient for fractional 
distillation, may be procured from Gerhardt, or from Eimer & 
Amend. — 





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and divided into four portions. One portion is 
heated to boiling, and then a slight excess of mer- 
curous nitrate solution added. Explain what takes 
place. The second portion is also heated to boil- 
ing, and a tolerably concentrated solution of silver 
nitrate added. Note what takes place. Explain. 
The third portion is evaporated to dryness, on a 
steam or water bath, with some powdered arsenic 
trioxide, and a little of the resulting mass heated 
in a test-tube when the characteristic odor of cacodyl 
oxide is given off. Explain. To the fourth portion 
add a little concentrated sulphuric acid and alcohol, 
and heat. Notice the odor. Explain. 

Write out all reactions, and show how you conld 
distinguish between formic and acetic acids. 

Describe the properties of acetic acid, and give 
some of the methods by which this subse may 
be detected in solution. 








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EXPERIMENT 18. 


Make up a solution containing ferric chloride, alu- 
minum, manganese, zinc, cobalt, and nickel chlorides. 
Nearly neutralize any free acid present with a solution 
of sodium carbonate (?). If a precipitate is formed dis- 
solve by adding a small quantity of acetic acid. Add 
enough of a concentrated solution of sodium acetate 
to convert all the metals present into acetates (taking 
care to avoid a large excess of the reagent), and boil 
the solution. Note what takes place. What is vola- 
tilized? Explain. Filter off the precipitate and test 
the filtrate for iron, aluminum, and the other metals. 
Draw your own conclusions from the results, and 
show how these facts could be utilized in analytical 
chemistry. Could you separate ferrous iron from 
ferric by this method? Explain. 


EXPERIMENT 19. 


To a mixture of equal parts of acetic acid and alco- 
hol in a test-tube add some concentrated sulphuric 
acid, and heat. Note what takes place. To what 
is the pleasant and characteristic odor due? What 
part does the sulphuric acid play? 

Write out reactions, and determine the delicacy 
of this reaction for the detection of small quantities. 
of acetic acid and salts of acetic acid. 





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EXPERIMENT 20. 


ACETYL CHLORIDE. 
(Hoop.) 


20 grams of glacial acetic acid are put into a dry (?) 
250 c.c. round-bottomed flask, the flask cooled with 
ice-water, and 80 grams of phosphorus trichloride 
(weigh this under the hood (?)) are gradually added, 
with constant shaking. Connect the flask with a 
return condenser, and heat it on a water-bath to 50° 
60° C. until almost all the hydrochloric acid gas has 
been expelled. The condenser is then turned down 
and the acetyl chloride distilled off, care being taken 
to protect the distillate from the action of the moist- 
ure in the air by means of a tube containing calcium 
chloride. The distillate is then placed in a small, dry 
distilling-flask, and redistilled with the same precau- 
tions as before. 

What remains in the flask in which the acetyl 
chloride was made? 

Determine all the properties of acetyl chloride, 
including color, odor, boiling-point, action on moist 
air. Add a few drops to some water in a test-tube 
and note what takes place. Explain. Put aside some 
of the chloride for Experiment 21. Save specimen 
in a small sealed tube and write out all reactions. 


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EXPERIMENT 21. 


Treat a few cubic centimeters of absolute alcohol 
with acetyl chloride and note what takes place. 
What gas is given off? What is formed? Explain. 
Repeat the experiment, using water instead of alcohol. 
Explain. What conclusions would you draw regard- 
ing the relation between water and alcohol from this 
experiment? What use is made of acetyl chloride 
in the laboratory? Write out all reactions. 





EXPERIMENT 22. 


ETHYL ACETATE. 


(Acetic Ether.) 


Arrange an apparatus! like that used in the 
preparation of ether (see Experiment 10). Into 
the flask A put 50 grams of concentrated sulphuric 
acid and 50 grams of absolute alcohol (95% will do). 
Heat till the temperature reaches 130°-140° C., and 
then add gradually through the separating-funnel a 
mixture of equal volumes of glacial acetic acid and 
absolute alcohol (95% will do). 

Separate the crude acetic ether from the water and 
wash’ with caustic soda solution; dehydrate in the 
usual manner with fused calcium chloride, and subject 
to fractional distillation. Determine the yield of 
ethyl acetate. 

Determine color, taste,-odor, boiling-point, specific 
gravity, solubility, inflammability, etc. Is there any 
analogy in the method of preparation of this acetic 
- ether and the method used to make ordinary ether? 
What else is formed here besides acetic ether? Save 
specimen. Write all reactions. 


1 Use a 1-liter flask. 





EXPERIMENT 28. 
SAPONIFICATION. 


Arrange an apparatus as shown in Fig. 8, page 
71, text-book, using a round-bottomed 500 c.c. flask. 
Calculate the amount of solid caustic soda neces- 
sary to decompose 20 grams of the ethyl acetate made 
in Experiment 22. Dissolve this amount plus 5 grams’ 
excess in 200 c.c. of water, add the 20 grams of ethyl 
acetate, and boil together on a sand-bath until the odor 
of ethyl acetate has disappeared. Then distil off 100 
c.c. of the liquid and examine the distillate. What 
does it contain ? 

Let the mixture in the flask cool, and when cold 
acidify with dilute sulphuric acid and again distil. 
What passes over now? Prove it. Write out all 
reactions. 

Given a mixture of ethyl acetate and ethyl! alcohol, 
show how you could determine the amount of ethyl 
acetate present. 










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EXPERIMENT 24. 


POTASSIUM CYANIDE. 
(Hoop.) 


100 grams of potassium ferrocyanide are dehydrated 
by heating the powdered salt in a porcelain dish in an 
air-bath to 110° C. until it ceases to lose weight. The 
dehydrated salt is powdered again if necessary, and 
then heated in an iron or copper retort provided with 
a cover and outlet-tube,. to a red heat with a triple 
burner or in a Fletcher gas-furnace. A gas comes 
off. Collect some over water and determine what 
it is. Continue heating the retort until gas ceases 
to come off, excluding air from the retort by keeping 
the outlet-tube under water. Then remove the out- 
let-tube from the water and let the retort cool. Take 
out the contents of the retort, grind in a mortar, 
and extract once or twice with boiling 50% alcohol. 
Filter and evaporate to crystallization. Determine 
solubility and crystal form of the salt. Does it re- 
semble potassium chloride in any way? Has it any 
odor? Explain. Isthesalt deliquescent? Does the ~ 
aqueous solution decompose? ‘Try it. What are the 
products? Is the aqueous solution alkaline? Ex- 
plain. Does an aqueous solution of the salt dissolve — 
the cyanides of mercury, gold, etc.? Try it. What 
use is made of this property ? Does the fused salt 





reduce metallic oxides? ‘Try it with some lead oxide 
(PbO) in a test-tube. Is the salt poisonous? Savea 
small specimen and keep the rest for use in Experi- 
ment 27. Write out all reactions. 


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EXPERIMENT 28.! 
(Hoop.) 


POTASSIUM FERRICYANIDE. 
1. 


Dissolve 50 grams of the crystallized potassium 
ferrocyanide in 150 c.c. of luke warm water in a 250 
c.c. flask. Filter the solution if necessary. Calcu- 
late the amount of bromine required to convert the 
50 grams of ferrocyanide into ferricyanide. Weigh 
off this amount of bromine under the hood, and add 
it gradually (by means of a separating-funnel, hay- 
ing its lower end drawn out into a capillary tube), 
to the solution of ferrocyanide, shaking constantly 
while the bromine is being added. ‘The solution 
is then evaporated to one-half its volume, and the 
ferricyanide allowed to crystallize out. The mother 
liquor, on being evaporated down, also yields a further 
crop of crystals. Save a specimen of the salt, and 
determine color, taste, crystal form, solubility, etc., 
of the potassium ferricyanide. Does the solution 
decompose in the light? Try it. What use is made 
of this fact? Is it a good oxidizing agent? Try 
it in alkaline solution with some lead oxide. Does 
potassium ferrocyanide contain water of crystalliza- 
tion? Does the ferricyanide? .To a small quantity of 


1 Method 3 has given the best results in this laboratory. 





a saturated solution of the ferrocyanide in a test-tube 
add an equal volume of fuming hydrochloric acid. 
Add two or three volumes of fuming hydrochloric 
acid to one volume of a saturated solution of the 
ferricyanide. Explain what takes place in each case. 
Write out all reactions. 


EXPERIMENT 25. 
POTASSIUM FERRICYANIDE. 
2. 


Dissolve 50 grams of crystallized potassium ferro- 
cyanide in 300 c.c. of water and add 10 grams of 
concentrated hydrochloric acid. Then run in from 
a burette a cold filtered solution of bleaching-powder 
until the solution no longer gives a precipitate of 
prussian blue with ferric chloride solution (testing 
the solution from time to time by taking out a drop 
or two). Neutralize any excess of hydrochloric acid 
present with precipitated chalk, filter the solution, 
and evaporate to crystallization. The first crop of 
crystals will be pure; the second may contain a small 
quantity of calcium chloride. 

Save a specimen of the salt, and examine it as 
directed in Experiment 25, 1. 






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EXPERIMENT 25. 
POTASSIUM FERRICYANIDE. 


3. 


Dissolve 26 grams of crystallized potassium ferro- 
cyanide in 200 c.c. of cold water, and add 8 c.c. of 
concentrated hydrochloric acid. Into this solution 
pour slowly a cold solution of 2 grams of potassium 
permanganate in 800 ¢.c. of water. The reaction is 
complete when a drop added to a solution of ferric 
chloride gives a brownish red color but no precipi- 
tate. Neutralize the excess of hydrochloric acid 
with chalk, filter, and evaporate on a water-bath to 
crystallization. 

Save a specimen of the salt, and examine it as 
directed in Experiment 25, 1. 


ic 





EXPERIMENT: 262 
POTASSIUM CY ANATE. 


Mix intimately 100 grams of dehydrated powdered 
potassium ferrocyanide with 75 grams of dry? pow- 
dered potassium bichromate, which has been previ- 
ously melted. <A little of this mixture is placed in 
a porcelain or, better, an iron dish and heated (con- 
siderably below redness) until the mixture begins 
to glow and blackens. The rest of the mixture is 
then added, little by little, each quantity being 
allowed to blacken before the next is added (com- 
plete oxidation of the cyanide to cyanate is thus 
effected). After cooling, the contents of the dish 
are extracted several times with boiling alcohol 
(450 cc. of 80% alcohol and 50 c.c. of methyl 
alcohol). Filter, and cool the alcoholic solution 
to 0°. Filter off the crystals formed, using a Witt 
plate and suction-pump. Dry on drying-paper. 
Continue the extraction until the black mass is ex- 
hausted. Yield, 42 % of the ferrocyanide used. To 
the alcoholic filtrate add 10 grams of ammonium 
sulphate in 20 c.c. of water, evaporate to dryness 
on the water-bath, extract with absolute alcohol, and 
proceed as directed in Experiment 47. Save a small 
specimen of the cyanate. Determine crystal form, 


1 Read carefully the directions in the text-book, page 85, and in 
the Chemical News, vol. 32, page 99. 
2 Heat some in a test-tube, and see that it gives off no water. 





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solubility, color, taste, odor, etc. Does the aqueous 
solution decompose on standing? ‘Try it. What 
are the products? Add some dilute sulphuric acid 
to a solution of the cyanate, and explain what takes 
place. Is there any resemblance between potassium 
cyanate and potassium hypochlorite? Show this by 
the method of formation, one from cyanogen and 
the other from chlorine and a solution of potassium 
hydroxide. Write out all reactions. 





EXPERIMENT 27. 
POTASSIUM SULPHOCYANATE. 


An aqueous solution of potassium cyanide (65 parts 
of the pure salt) is heated with flowers of sulphur (82 
parts) in a round-bottomed flask connected with a — 
return-condenser, until all the sulphur is dissolved. 
Filter the solution and evaporate to crystallization. 
Drain off the crystals and repeat the evaporation with 
the mother liquor. Use 20 grams of the potassium 
cyanide made in Experiment 24 and calculate the 
amount of sulphur necessary to form the sulphocya- 
nate. 

Determine properties of the salt, including color, 
taste, odor, crystal form, solubility, melting-point, 
etc. What takes place when the crystals are left 
exposed to the air? Is there any analogy between 
the formation of the cyanate (Experiment 26) and 
the sulphocyanate? What use is made of the sulpho- 
cyanate in the laboratory? Heat some of the salt in 
a porcelain crucible and note changes in color. Let 
cool and note any changes. Make some mercuric 
sulphocyanate, dry, roll into small pellets, and ignite 
(Pharaoh’s serpents). Explain. 

Save a specimen of the potassium salt and write 
out all reactions. 





EXPERIMENT 28. 


Dissolve 5 grams of potassium sulphocyanate in 
water, and note any change in the temperature of 
the water. Explain. 


EXPERIMENT 29. 
AMMONIUM SULPHOCYANATE. 


Mix 60 grams of alcohol (95%), 80 grams of am- 
monia solution (sp. gr. 0.912), and 35 to 40 grams 
of carbon bisulphide,! and allow to stand in a glass 
stoppered bottle for one or more days until all the 
carbon bisulphide has dissolved. ‘The process may 
be hastened by shaking the bottle from time to time. 
When all the carbon bisulphide has dissolved, evapo- 
rate the solution at a gentle heat on a steam or water 
bath (Hood) to one-third of the original volume. 
What goes off? Filter off any sulphur that may 
separate out while the solution is hot. On cooling, 
ammonium sulphocyanate crystallizes out. Filter off 
the crystals and repeat the evaporation with the 
mother liquor. 

Determine crystal form, solubility, color, taste, 
odor, and melting-point of the salt. 

Save a specimen of the salt, and write out all 
reactions. 


1 Carbon bisulphide is very inflammable. In working with it always 
avoid any flames. 





EXPERIMENT 30. 


PHENYL ISOCYANIDE. 
(See text-book, page 91.) 


Dissolve a small quantity of solid caustic potash 
in alcohol in a test-tube and add one or two drops of 
aniline. Then add a drop of chloroform to 100 -c.c. 
of distilled water in a small flask, and shake the mix- 
ture thoroughly. Now add a drop or two of this 
water saturated with chloroform to the caustic potash 
solution containing the aniline, and heat the test-tube 
under the hood. The odor is that of phenyl isocya- 
nide. 

This reaction is a very delicate one, and may be 
used to detect the presence of any primary amine or 
of chloroform. Is aniline an amine? Write the 
reaction. What is the object of the caustic potash ? 






4 
or 


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EXPERIMENT 831. 
FLASHING-POINT OF KEROSENE. 


Make an apparatus like the one figured on page 
112 of the text-book, but of the following dimen- 
sions: A is a glass cylinder 35 m.m. wide and 175 
m.m. high, and has a mark 60 m.m. from the bottom, 
and another at 70 m.m. from the bottom. The kero- 
_sene is poured in up to the lower mark. The cylin- 
der is placed in a water-bath (a beaker filled with 
water up to the 60 m.m. mark on the cylinder), the 
temperature of which is raised slowly (one degree in 
two or three minutes). At each degree air is passed 
through for five seconds so rapidly that the foam on 
the kerosene reaches the second mark. At the same 
time a small flame is held at the mouth of the vessel 
A. When the vapor ignites and a bluish flame runs 
down to the surface of the oil, note the temperature. 
The first determination gives only approximate re- 
sults. The kerosene is replaced by a fresh supply, 
and the observations are begun at a temperature a 
little below that obtained in the first determination. 
The temperature of the kerosene and that of the 
water-bath should differ only by one degree. Deter- 
minations should agree to within 4°. The propor- 
tions given for the cylinder and the directions must 
be observed to get good results. Determine the 
flashing-point of several-specimens of kerosene, and 
particularly of that kerosene you burn at your room. 
See if it is above the flashing-point required by law. 





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. EXPERIMENT 32. 
ALDEHYDE. 


Mix equal weights (1 gram) of dry calcium for- 
mate and dry calcium acetate. Distil from a test- 
tube fitted with a delivery-tube. Collect some of 
the distillate in water. What does the water con- 
tain? Prove it. Write out the reaction. 


EXPERIMENT 388. 
PALMITIC AND STEARIC ACIDS. 


Dissolve 10 grams of solid caustic potash in 150 
c.c. of alcohol in a 250 c.c. flask and filter. Melt 
in a porcelain dish on a water-bath 10 grams of lard 
and then add the alcoholic solution of caustic potash. 
Evaporate to syrupy consistency slowly on the water- 
bath, with constant stirring. Convince yourself that 
the substance left is soap (’?). 

Dissolve the syrupy mass in a small quantity of 
cold water, and filter if necessary. Add to a little 
of this soap solution a few drops of a solution of 
(1) calcium sulphate, (2) magnesium sulphate, and 
(3) calcium acid carbonate, and explain what takes 
place in each case. What is meant by the terms © 
permanent and temporary hardness of water? How 
do you determine the hardness of a water? How 
could you make a hard water soft? 





Acidify the soap solution remaining with dilute 
sulphuric acid. A precipitate is formed. What is 
it? Filter off the precipitate and drain it thoroughly. 
Recrystallize it from alcohol and determine its melt- 
ing-point and properties. Has the substance acid 
properties? Prove it. 

Neutralize the filtrate exactly with a solution of 
potassium carbonate or potassium hydroxide, evap- 
orate to dryness on the water-bath, and extract with 
absolute alcohol. Filter the alcoholic solution, and 
evaporate off the alcohol on the water or steam bath. 
What is the syrup which remains? Prove it. 

Save specimens of the acids and the syrup. Write 
out all reactions after glycerol has been considered. 


oe? 


2 ris Ae 





EXPERIMENT 34. 


OXALIC ACID. 


(Hoop.) 


In a long-necked flask, of about 1-liter capacity, 
heat gently 25 grams of cane sugar and 125 grams 
of nitric acid (sp. gr. 1.245). Gases are evolved. 
_ Explain. After the reaction is over, evaporate the 
solution to crystallization and let cool. Filter or 
pour off the mother liquor and add to it a smaller 
quantity of nitric acid, heat, and again evaporate to 
crystallization. Filter off the crystals, drain com- 
pletely on a Witt plate, and recrystallize from dis- 
tilled water. 

Determine color, taste (poison), odor, solubility, 
crystal form, etc., of the acid. Is it a strong acid? 
Try it. Does it contain water of crystallization? 
Prove it. Does it sublime when heated? ‘Try it. 
Is it a reducing agent? Why? Heat some of the 
acid in a small flask under the hood with concen- 
trated sulphuric acid and prove that both oxides of 
carbon are set free. What does the acid yield when 
heated with glycerol? What is potassium tetrox- 
alate? What use is made of this salt in the labo- 
ratory ? | 

Save a specimen of oxalic acid. Write out reac- 
tions after glucose has been considered. 






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EXPERIMENT 385. 


Dissolve some oxalic acid in water and add some 
dilute sulphuric acid (?). Now run in a little of a 
dilute solution of potassium permanganate and note 
what takes place. What becomes of the perman- 
ganate and of the oxalic acid? Prove it. Write 
out the reaction and calculate how much perman- 
ganate would be necessary to oxidize 5 grams of 
erystallized oxalic acid. 


EXPERIMENT. 36. 
BASIC FERRIC SUCCINATE. 


Dissolve about a gram of succinic acid in water, 
and neutralize carefully with dilute ammonia solution. 
Add some of this solution of ammonium succinate to 
a neutral solution of manganese chloride and ferric 
chloride, and boil. A precipitate is formed. What 
is it? Filter it off, and test the filtrate for iron and 
for manganese, and draw your own conclusions from 
the results. Has the filtrate an acid reaction? Explain. 
Write out all reactions. Compare results with those 
obtained in Experiment 18. 





EXPERIMENT 37. 
GLYCEROL. 


Determine color, taste, odor, solubility, etc., of 
glycerol. Is it hygroscopic? Can it be distilled 
under ordinary pressure? What is its boiling-point? 
Does glycerol dissolve caustic potash, lead oxide 
(PbO), or calcium oxide? Explain. 

Put 20 c.c. of glycerol into a 250 c.c. distilling- 
flask and distil with superheated steam. Does the 
glycerol distil with the steam? Prove it — see 
Roscoe and Schorlemmer’s Treatise on Chemistry, 
Vol. III. Part I. page 350, for a method of detecting 
glycerol. 

Compare reactions of the glycerol obtained in Ex- 
periment 83 with the ordinary glycerol. Are the 
two identical? Explain the formation of formic acid 
by the decomposition of oxalic acid in glycerol by 
heat. | 







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EXPERIMENT 388. 
FEHLING’S SOLUTION. 


Dissolve 8.5 grams of crystallized copper sulphate 
in 50 c.c. of water to which one drop of sulphuric 
acid has been added. Bottle and label ‘ Copper Sul- 
phate Solution.” Take 17.5 grams Rochelle salt 
(potassium sodium tartrate) and dissolve in 35 c.c. 
of water. Filter and add a solution of 5 grams of 
caustic soda in 10 c.c. of water. Make the solu- 
tion up to 50 c.c., bottle and label “Alkaline Tar- 
trate Solution.” For use, mix equal parts of these 
solutions. 

Into a small porcelain dish put 5 e.c. of each of 
the above solutions. Heat nearly to boiling and add 
a few drops of a one per cent solution of glucose. 
Note what takes place. Continue to add the glucose 
solution drop by drop until the precipitate settles 
and leaves the solution clear and colorless. Filter 
off the precipitate, wash with hot water, dry, and save 
specimen. What is this precipitate? What becomes 
of the glucose? Does a solution of glucose reduce an 
ammoniacal solution of silver oxide? Try it. What 
conclusions do you draw from these facts as to the 
constitution of glucose? Write out all reactions. 





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EXPERIMENT 39. 


Dissolve 1.5 grams of cane sugar in 200 c¢.c. of 
distilled water. Test a little of this solution with 
the Fehling’s solution, proceeding as directed in Ex- — 
periment 88. Does any reduction of the copper solu- 
tion take place? Now add to the sugar solution 
about ten drops of hydrochloric acid (sp. gr. 1.11), 
and heat the mixture on the water-bath to 100° . 
for half an hour. Neutralize the solution exactly 
with a dilute solution of sodium carbonate, and again 
test it with Fehling’s solution. Does any reduction 
take place now? What is the function of the hydro- 
chloric acid? Explain. 

Given a solution containing both cane sugar and 
glucose, show how you could estimate both by means 
of Fehling’s solution. 





EXPERIMENT 40. 
CELLULOSE. 


Treat some absorbent cotton with dilute caustic 
soda solution and warm gently; then wash with 
water, and repeat the process, using dilute hydro- 
chloric acid. Again wash with water, then boil 
with alcohol once or twice, pour off the alcohol, and 
digest with ether. Remove the ether and dry. This 
treatment removes incrusting substances and leaves 
a comparatively pure cellulose. Has cellulose any 
crystalline form? Is it soluble in any of the ordi- 
nary solvents? Try it. Dissolve some pure cellulose 
(Swedish filter-paper) in a small quantity of concen- 
trated sulphuric acid; dilute with much water, and 
boil the solution for half an hour. Neutralize exactly 
with an alkali and test with Fehling’s solution. 
Does any reduction take place? Explain. Write 
out all reactions. Save a specimen of pure cellu- 


lose. 


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EXPERIMENT 41. 
SCHWEIZER’S REAGENT. 


Dissolve 10 grams of crystallized copper sulphate 
in 150 to 200 cc. of water in a’ 500 ec.c. flask, 
and add to the cold solution 5 c.c. of a solution of 
ammonium chloride. Precipitate cupric hydroxide 
from this solution by adding a slight excess of sodi- 
um hydroxide solution. Then wash by decantation 
with cold water, and finally on a cloth filter, until the 
wash water no longer gives a precipitate with barium 
chloride solution. To 30 c.c. of ammonia solution 
add this washed copper hydroxide as long as it will 
dissolve, and filter the solution through glass wool. 
This is an ammoniacal solution of copper hydroxide, 
and is known as Schweizer’s Reagent. Will it dis- 
solve cellulose? Try it with some ordinary cotton, 
with filter-paper, and with some pure cellulose. - 
Dilute the solutions thus obtained with water, filter 
through glass wool (?), and acidify with dilute hydro- 
chloric acid. What takes place? 

It is essential for the success of the above experi- 
ment that the copper hydroxide should be washed 
free from salts and preferably out of contact with 
the air. 

Explain the Willesden process of water-proofing 
cotton fabrics. (See Watt’s Dictionary of Chem- 
istry, revised edition, or Thorpe’s Dictionary of 
Applied Chemistry, under Cellulose.) 





EXPERIMENT 42. 
STARCH. 


Grind in a small mortar a gram of arrowroot 
starch with some distilled water. Pour the creamy 
mass thus produced into 500 c.c. of boiling distilled 
water contained in a porcelain dish, stirring con- 
stantly while the starch is being added. A few 
drops of this solution is then added to a liter of 
water and one drop of a solution of potassium iodide. 
Does any color appear? Adda drop or two of freshly 
prepared (?) chlorine water and note what takes 
place. Explain. Is the color destroyed when chlo- 
rine water is added in excess? when alkalies are 
added? by sulphurous acid? by hydrogen sulphide? 
by sodium thiosulphate? Try it with each reagent 
with a small quantity in a test-tube. Explain and 
write out all reactions. Does the color disappear 
on heating? Heat some in a test-tube, and then 
cool. Does the color reappear on cooling? Explain. 
From the above conduct state whether the starch- 
iodine compound is a chemical compound or not. 
Test the delicacy of this reaction for iodine and for 
starch. 


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EXPERIMENT 48. 


Study the action of bromine water on some of the 
starch solution made in Experiment 42. Does it 
give any color? Add a few drops of a solution of 
potassium bromide to some of the starch paste solu- 
tion, dilute with water, and then add a few drops of 
chlorine water. What takes place? Why is the 
chlorine water added? Is the starch-bromine com- 
pound destroyed by heat? Try it. Is this reaction 
between the starch and bromine as delicate as the 
one with iodine? Could you distinguish between 
chlorine, bromine, and iodine by means of starch 
solution ? 


EXPERIMENT 44. 


- Test some of the starch paste solution made in 
Experiment 42 with Fehling’s solution. Does it 
reduce it? Add 5 cc. of concentrated hydrochloric 
acid to 200 c.c. of the starch paste solution, and heat 
to boiling in a flask connected with a return con- 
denser for an hour and a half. When cold, neu- 
tralize with sodium carbonate solution, and examine 
with Fehling’s solution. Does it reduce the Fehl- 
ing’s solution now? Does the solution now contain 
any starch? Test it with a solution of iodine in 
potassium iodide solution. Explain, and write out 
all reactions. 


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EXPERIMENT 45. 
DIETHYL OXALATE AND OXAMIDE. 


Grind 100 grams of crystallized oxalic acid to 
powder, and dehydrate by heating in an air-bath 
to 100°C. Weigh the anhydrous oxalic acid, and 
add to it an equal weight of absolute alcohol. Boil 
this mixture in a flask connected with a return-con- 
denser for four hours. Then transfer to a distilling- 
flask, and distil until the temperature reaches 110° C. 
Add to the residue left in the distilling-flask a volume 
of absolute alcohol equal to that of the distillate, and 
again boil for four hours in the apparatus first used. 
Once more transfer to the distilling-flask, and distil. 
When the temperature reaches 145° C., change the 
receiver, increase the heat, and distil off the residue 
as quickly as possible. From the first fractions separate 
the ethyl formate, by fractional distillation, using a 
Hempel or Vigreux distilling-tube, and, from the 
second, the diethyl oxalate. 

Determine the boiling-point, color, taste, odor, 
specific gravity, inflammability, etc., of both sub- 
stances, and explain their formation. 

To the alcoholic solution of diethyl oxalate, result- 
ing from the fractionation, add some concentrated 
ammonia. What takes place? Filter off the pre- 
cipitate, wash, and examine. Boil some with a little 
caustic potash solution in a test-tube. Does it dis- 





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solve? What gas comes off? What remains in 
solution? Prove it. 

Save specimens of ethyl formate, diethyl oxalate, 
and oxamide. Write out all reactions. 


EXPERIMENT 46. 


UREA FROM URINE. 
(Hoop.) 


Evaporate 3 liters of fresh urine to a thick syrup 
in a porcelain dish, first on a gas-stove, then on 
the water-bath. When cold, add concentrated nitric 
acid to the residue, and precipitate the urea con- 
tained in the syrup in the form of the nitrate. Filter 
off the precipitate, using a Witt plate and suction- 
pump. Dissolve the crude nitrate in boiling water, 
and decolorize the solution by adding a dilute solu- 
tion of potassium permanganate, drop by drop. Then 
evaporate the solution to crystallization, filter, and 
continue the evaporation with the mother liquor. 
Drain, and dry the urea nitrate, and save a small 
specimen. 

Weigh the nitrate, dissolve in water, add a slight 
excess of powdered barium carbonate (calculated), 
and evaporate to dryness on the water-bath. From 
the dry residue extract the urea by boiling with 
strong alcohol (95%), filter, and evaporate to crys- 





tallization. Weigh the urea obtained, and calculate 
the percentage in the urine used. Determine crystal 
form, melting-point, solubility, color, taste, odor, ete. 
Heat a little of the dry substance. What is formed ? 
Treat a concentrated solution in a test-tube with a 
solution of oxalic acid, and explain what takes place. 
Add a dilute solution of urea to a dilute solution 
of mercuric nitrate. What takes place? Add a 
little mercuric oxide to a solution of urea. What 
takes place? 

Save a specimen of urea, and write out all re- 


actions. 





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EXPERIMENTS 47 AND 48. 
UREA FROM AMMONIUM CYANATE. 


Dissolve 20 grams of the potassium cyanate, ob- 
tained as directed in Experiment 26, in cold (?) water 
and add to it a solution of ammonium sulphate, con- 
taining just enough ammonium sulphate to change the 
potassium cyanate to potassium sulphate (calculated). 
Evaporate the solution to dryness on the water-bath, 
and extract the residue with boiling absolute alcohol. 
Filter and evaporate to crystallization. Weigh the 
urea obtained, and see how it agrees with the amount 
required by theory. Compare the artificial urea with 
that obtained from urine, and prove their identity 
by a determination of melting-points and other physi- 
cal and chemical properties. What is formed when 
ammonium sulphocyanate is heated to its melting- 
point? 

Save a specimen of the urea, and write all re- 


actions. 
1 Do this experiment with Experiment 26. 





EXPERIMENT 49. 


Dissolve 8 grams of caustic soda in 100 c.c. water, 
and add 2 c.c. of bromine. What does this solution 
contain? Make a solution of both the artificial and 
the natural urea, and add to some of the above 
solution. A gas is given off. Collect some, and 
determine what it is. What remains in solution? 
Urea may be determined in urine by this method. 
Explain process, and write out reactions. 

Dissolve a small quantity of sodium nitrite in 
water, and add to it an acidified solution of urea. 
What takes place? Explain. Reaction? 


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EXPERIMENT 51. 
ETHYLENE AND ETHYLENE BROMIDE. 


Place 50 to 60 c.c. of syrupy phosphoric acid (sp. 
or. 1.75) in a 200 c.c. distilling-flask, fitted with a 
cork carrying a thermometer and a separating-funnel, 
both reaching to the bottom of the flask. Heat the 
flask on a sand-bath and allow the phosphoric acid 
to boil for a few minutes until its temperature reaches 
200°, when ethyl alcohol is allowed to enter very 
slowly through the separating-funnel. Ethylene is 
evolved and by keeping the temperature between 
200 and 220° a continuous supply of the gas may be 
obtained. Conduct the gas through an empty wash- 
bottle (150 c.c. capacity) surrounded with a freezing 
mixture and then through another wash-bottle con. 
taining a small quantity of concentrated sulphuric 
acid, Collect some of the gas over water. Deter- 
mine odor, taste, color, inflammability, solubility, etc. 
Mix 1 volume of the gas and 3 of oxygen in a stout 
cylinder, and apply a flame. What takes place? 
After enough gas has been collected for the above 
experiments, pass it into another wash-bottle con- 
taining a layer of bromine ! } inch deep, covered with 
water, and then into a bottle containing 20% ‘sodium 
hydroxide solution (?). When the bromine has been 
decolorized (explain), separate from the water, wash 
the resulting product with dilute caustic soda solution, 


1 Bromine should always be handled very carefully and under the 
hood. — - 





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then with water, separate from the water, dry with 
calcium chloride, and distil, noting the temperature. 

Determine its boiling-point, color, taste, specific 
gravity, odor, solubility, etc. Does it solidify on 
cooling? What is formed when it is treated in alco- 
holic solution with granulated zinc? Prove it. Save 
specimen of ethylene bromide, and write out all 


reactions. 


EXPERIMENT 52. 


ACROLEIN. 
(Hoop.) 


Heat in a small flask a mixture of 5 grams of 
anhydrous glycerol and 10 grams of powdered fused 
acid potassium sulphate. Pass the gases evolved 
through a bent tube into water contained in another 
small flask. Note the odor. What produces it? 
Does the aqueous solution reduce an ammoniacal 
solution of silver oxide? ‘Try it. Explain. Save 
tube containing mirror, and write out all reactions. 


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EXPERIMENT 53. 
ACETYLENE. 


Put 10 grams of calcium carbide (CaC,) in an 
Erlenmeyer flask provided with a separating-funnel 
and a delivery-tube, and add water drop by drop. 
Examine the gas evolved as directed in Experiment 
54. Pass some of the gas through an alcoholic solu- 
tion of iodine. What takes place? Explain. Pre- 
pare an ammoniacal solution of silver oxide ! and pass 
the gas through it until the reaction is complete. A 
precipitate is formed. What is it? After sufficient has 
collected, filter it off, wash with water, and examine. 
Determine color, solubility, etc. Does it resemble 
silver chloride in any respect? Explain. Does it ex- 
plode when heated or on percussion? Dry some care- 
fully, and try it. Write all reactions. Save silver solu- 
tions, and put into bottle marked “Silver Residues.” 

1 To make ammoniacal silver oxide solution, proceed as follows: 
Dissolve 5. grams of silver nitrate in water, add cautiously dilute 
ammonia solution till the precipitated silver oxide is just dissolved. 


An ammoniacal solution of cuprous chloride may be substituted for 
the silver solution. 





EXPERIMENT 54. 


Put the precipitate obtained in Experiment 53, 
together with a little water, into a small flask pro- 
vided with a funnel-tube and delivery-tube. Slowly 
add, through the funnel-tube, moderately concen- 
trated nitric acid, and warm the flask gently if 
necessary. <A gas is evolved. After the air has 
been expelled, collect the gas over water in cylin- 
ders, and examine. What is it? Has it any odor? 
Does it burn? Does it form an explosive mixture 
with air? Try it. Does it unite with bromine? 
Try it with some bromine water. Is it soluble in 
water or alcohol? Is it lighter or heavier than air? 
What remains in the flask from which the gas was 
evolved? Explain and write all reactions. Is acety- 
lene an acid? 

Save silver salts, and put in proper bottle. 

1 Use great care in this experiment. It is better to light the 


bubbles of gas formed when a small piece of calcium carbide is 
dropped into a beaker full of water. 





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EXPERIMENTS 55 AND 57. 
BENZENE. 


Grind together intimately in a mortar 50 grams 
of benzoic acid and 100 grams of good soda-lime. 
Distil the mixture from an iron retort, connecting 
the long delivery-tube of the retort with a bent 
adapter, and surrounding the receiver with ice-water. 
Heat the retort with a triple burner, and continue 
the heating until liquid ceases to distil. Separate 
the oil from the water in the distillate, wash with 
dilute caustic soda solution (?), dry with fused cal- 
cium chloride, as usual, and xe-distil from a small 
distilling-flask, noting the temperature at which it 
boils. What is the substance thus obtained ? 

Determine its boiling-point, specific gravity Clighter 
or heavier than water), odor, color, taste, inflamma- 
bility, etc. Does it solidify when cooled to 0°? 
Try it. Is it a good solvent? Try it. What re- 
mains in the retort in which this substance was 
made? Prove it. Is there any analogy between 
this method of making benzene and the method of 
making marsh gas? Save a specimen of the ben- 
zene, and write out all reactions. 





EXPERIMENT 56. 
BENZENE AND TOLUENE. 


Put 800 c.c. of light oil into a 1-liter distilling- 
flask connected with a condenser and receiver. Dis- 
til until the temperature reaches 125°. Put the 
distillate into a large separating-funnel, and shake 
it several times with small quantities of concen- 
trated sulphuric acid. Remove the acid, wash with 
water, and then shake once or twice with caustic 
soda solution. Remove the soda solution, wash 
again with water, dry with fused calcium chloride 
in the usual manner, and subject the product to frac- 
tional distillation, using a Hempel or Vigreux distilling- 
tube. Continue the fractionation until a portion is 
obtained boiling at about 80°, and another at about 
110°. Prove that the first fraction is identical with 
the benzene obtained in Experiment 58. What is 
the second fraction? What is the object of the 
shaking with sulphuric acid and the caustic soda 
solution? Save specimens of both substances. 





EXPERIMENT 58.1 


NITROBENZENE. 


(Hoop.) 


A cooled mixture of 60 grams of concentrated 
nitric acid (sp. gr. 1.42) and 80 grams of ordinary 
concentrated sulphuric acid (sp. gr. 1.84) is slowly 
and carefully added from a separating-funnel, drop 
by drop, and with constant shaking, to 50 grams 
of benzene, contained in a 4-liter flask, care being 
taken to prevent the temperature rising above 50°. 
Gases come off. What are they? Explain. When 
all the acid has been added, heat the mixture on @ 
boiling-water or steam bath for half an hour, shak- 
ing the flask constantly. After cooling, pour the 
mixture into half a liter of cold water, and separate 
the acid layer by means of a separating-funnel. 
Wash the oil remaining several times with water, 
and then with dilute soda solution, drawing off the 
oil each time from the bottom of the funnel. Wash 
finally with water, separate the oil from the water 
as completely as possible, dry with calcium chloride 
in the usual way, and subject to distillation, using 
a plain tube as a condenser. What comes over? 
What is the brownish residue left in the flask? 
Determine the boiling-point, specific gravity, solu- 
bility, color, taste, odor, etc., and yield of the nitro- 


1 The vapor of nitrobenzene is poisonous, and care should he 
taken not to inhale it. 





benzene obtained. Does it solidify on cooling? Why 
is the sulphuric acid added in the preparation of 
the nitrobenzene ? 

Write out all reactions, save a small specimen 
of the substance, and use the rest in the following 
experiments. | 


EXPERIMENT 59.1 


DINITROBENZENE. 
(Hoop.) 
if 


Add gradually 1 volume of benzene (50 grams) 
to 2 volumes of fuming nitric acid (sp. gr. 1.52), 
warming the mixture toward the end of the opera- 
tion until all the benzene has gone into solution. 
Allow the mixture to cool somewhat, then add 3.8 
volumes of concentrated sulphuric acid, and boil for 
some time. After cooling, pour the mixture slowly 
into water. Filter off the crystal mass on a Witt 
plate, wash with water until free from acid, drain 
completely, and recrystallize from hot alcohol. 

Determine the melting-point, crystal form, solu- 
bility, color, odor, taste, etc. What substances re- 
main in the mother liquor? Save a specimen of the 
crystals, and write out all reactions. 


1 Make dinitrobenzene by either method. The second one has 
given the better results in this laboratory. 





EXPERIMENT 59. 


DINITROBENZENE. 
(Hoop.) 
2. 


15 grams of nitrobenzene are gradually added from 
a separating-funnel to a mixture of 25 grams of con- 
centrated nitric acid (sp. gr. 1.47) and 40 grams 
of concentrated sulphuric acid (sp. gr. 1.84), con- 
tained in a flask of 500 c.c. capacity. The flask 
should not be cooled, but should be frequently 
shaken during the addition of the nitrobenzene. 
When all the nitrobenzene has been added, heat the 
flask gently on a sand-bath until red fumes cease 
to be given off and the reaction is complete. The 
flask should be shaken constantly during the heat- 
ing. After cooling, pour slowly into a liter of water. 
Filter off the crystals on a Witt plate, using a suction- 
pump to drain thoroughly, wash free from acid, 
drain, and recrystallize from hot alcohol. 

Determine the melting-point, crystal form, solu- 
bility, color, odor, taste, etc., of the crystals. What 
substances remain in the alcoholic mother liquor? 
Save a specimen of the crystals, and write out all 
reactions. | 


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EXPERIMENT 60. 
ANILINE. 


Put 150 c.c. of water, 55 grams of finely divided 
east-iron filings,! and 40 grams of nitrobenzene into 
a 1500 c.c. round-bottomed flask connected with a 
return-condenser. Add 20 grams of concentrated 
hydrochloric acid through the inner tube of the con- 
denser. Heat gently with a small flame until the 
reaction begins. After the first violent reaction is 
over, heat the flask gently, and continue until the 
odor of nitrobenzene has disappeared (about 10 hours). 
Then add water (250 c.c.) to the flask, and distil with 
steam. Jf the distillate has the odor of nitrobenzene, 
add cone. hydrochloric acid until the aniline has 
entirely dissolved, and extract the nitrobenzene by 
shaking with ether. Then remove the ether, concen- 
trate the aqueous solution, and add caustic soda solu- 
tion to alkaline reaction, put into a separating-funnel, 
and extract two or three times with small quantities of 
ether. If the distillate does not smell of nitroben- 
zene, and a little of the oil dissolves vompletely in 
hydrochloric acid, simply extract it once or twice 
with ether. Separate the ether extracts from the 
water as completely as possible, dry with solid caustic 
potash in the usual manner, place in a distilling-flask, 
and distil off the ether (with care). Finally, in- 
crease the heat, and distil the aniline. Determine 


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its boiling-point, solubility, specific gravity (lighter 
or heavier than water), color, odor, taste, ete. Has 
the solution in water an alkaline reaction? Try it. 
Does aniline dissolve in dilute acids? Explain. Is 
it affected by the ight? Does its aqueous solution 
precipitate salts of zinc, aluminum, and iron? ‘Try 
it. Explain. Does aniline decompose ammonium 
salts? Heat some with a solution of ammonium 
chloride. 

Save a small specimen of aniline, and use the rest 
in Experiments 61 and 62. Write out all reactions. 
(See Roscoe and Schorlemmer’s Treatise on Chem- 
istry, Vol, III. page 196, or Gattermann’s Practical 
Methods of Organic Chemistry (second American 
edition), page 191, for explanation of the process. ) 





EXPERIMENT 61. 


To a dilute aqueous solution of some of the aniline 
made in Experiment 60 add a few drops of a filtered 
solution of bleaching-powder, and note the result. 
Explain. Very dilute solutions of aniline give but 
a slight coloration, but a color is brought out by 
adding a few drops of a dilute solution of ammonium 
sulphide to the mixture. Try it, and test the deli- 
cacy of this last reaction. 

To a solution of aniline in concentrated sulphuric 
acid add a few grains of solid potassium bichromate, 
and warm the test-tube gently. What takes place? 

What other reactions have you already had which 
might be used to detect the presence of aniline? 
Write out all reactions after the aniline dyes have 
been considered. 








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EXPERIMENT 62. 
BENZENE-DIAZONIUM CHLORIDE. 


Suspend 10 grams of aniline hydrochloride in 30 
erams of glacial acetic acid and 15 c.c. of absolute 
alcohol, cool below 10° and add, with constant stir- 
ring and slowly, 10 grams of amyl nitrite,! taking 
care that the temperature does not rise above 10°. 
The suspended aniline hydrochloride quickly dis- 
solves and the diazotization is complete when a 
small portion of the mixture, removed with a pipette, 
no longer gives a yellow color when treated with 
a solution of sodium acetate (?). Then treat with 
an equal volume of ether, keeping the temperature 
below 0°. Filter off the crystals of the diazonium 
chloride on a Witt plate by suction, wash with a 
little ether, and dry in the air on filter-paper.2, Weigh 
the dry salt and determine the yield. 

Determine the color, solubility, and crystal form 
of the salt. Does it decompose on standing in the 
light? Does it act like a substituted ammonium 
salt towards solutions of platinum chloride and gold 
chloride? Does it give a perbromide with a solution 
of bromine in potassium bromide? Does NH,Br 
form a perbromide ? 

1 Do not breathe the vapor of amy] nitrite (?). 

2The dry salt is very explosive, and great care must be 
exercised in handling it. Wash out all vessels containing it 


at once with water and use up all of the material as soon as 
possible. 


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(a) Heat some of the dry salt cautiously on plati- 
num foil, and note what takes place. Does the salt 
explode on percussion? ‘Try it. 

(6) Boil some with absolute alcohol, and describe 
what takes place. What are the products of the 
reaction ? 

(ce) Boil a little of the dry salt with water. What 
takes place? What are the products of the reaction ? 
Prove it. 

(d) Treat a solution of dimethylaniline in water 
with an aqueous solution of benzene-diazonium chlo- 
ride and observe what takes place. Explain. 

(e) Dissolve 10 grams of aniline in a mixture of 
50 grams of concentrated hydrochloric acid*(sp. gr. 
1.19) and 150 c.c. of water. Cool the mixture with 
ice-water below 10° and add gradually, with constant 
shaking, a solution of 9 grams of sodium nitrite in 
50 c.c. of water, until an excess of nitrous acid is 
shown to be present by the blue color the solution 
imparts to starch-potassium-iodide paper. Explain. 
What does this solution now contain? When the 
diazotization 1s complete (?) transfer the solution to 
a 2-liter balloon flask, cool to 10°, add a solution of 
25 grams of potassium iodide in 40 c.c. of water and 
allow the mixture to stand for two hours at about 
10°. Then heat it gently on the water- or steam- 
bath until the evolution of nitrogen ceases. Explain 
what takes place here. Make the liquid strongly 
alkaline with caustic soda solution (?), distil the oil 





with steam, separate it from the water by means of 
a separating-funnel, dry with calcium chloride, and 
redistil it, noting the temperature at which it boils. 
What is the substance thus obtained? Determine 
the color, odor, action of light, solubility, boiling- 
point, and specific gravity (lighter or heavier than 
water) of the liquid. Save the specimen and deter- 
mine the yield. Write out all reactions. 





EXPERIMENT 63. 
BENZENE-SULPHONIC ACID. 


Place 300 grams of fuming sulphuric acid (contain- 
ing 15 % SO,) in a 500 c.c. flask and add gradually, 
by means of a separating-funnel, and with constant 
shaking and thorough cooling with water, 80 grams 
of benzene. Before adding each new quantity of 
the benzene, see that the last portion, which at first 
floats on the surface of the acid, dissolves on shaking, 
and keep the temperature of the acid below 50° (?). 
When all the benzene has dissolved, which will re-- 
quire about 15 minutes, cool the mixture to 0°, place 
it in a separating-funnel and add it, gradually and 
with constant stirring, to a solution of 200 grams of 
sodium chloride in 800 c.c. of water. The sodium 
chloride solution is kept at 0° by surrounding it 
with ice-water. The sodium salt of benzene-sul- 
phonic acid separates at once or, on the addition of 
a few crystals and thorough stirring, in the form of 
lustrous leaflets. After allowing the mixture to 
stand for some time at 0°, filter off the crystals on 
a Witt plate by suction, drain off the mother liquor 
thoroughly, dry in fhe air on drying-paper as com- 
pletely as possible. Weigh the dry material and deter- 
mine the yield of the sodium benzene-sulphonate. 
In order. to obtain sodium benzene-sulphonate free 
from sodium chloride, recrystallize 5 grams of it from 
absolute alcohol in which sodium chloride is practically 





insoluble. Determine the amount of sodium chloride 
present in the mixture in order to estimate the true 
yield of sodium benzene-sulphonate obtained. Save 
the specimen of the crystallized sodium salt and deter- 
mine its color, crystal form, and solubility. Does it 
contain water of crystallization? Use the dry salt in 
the following experiments and write out all reactions. 





EXPERIMENT 64. 


BENZENE SULPHON-CHLORIDE AND 
SULPHONAMIDE. 


(Hoop. ) 


Grind together, in a porcelain dish, equivalent 
* quantities (20 grams) of dry sodium benzene-sul- 
phonate and phosphorus pentachloride (24 grams). 
What is formed? Then after cooling add ice-water, 
and wash the oil free from inorganic salts. Separate 
as completely as possible from the water, weigh, take 
out a small specimen, and to the rest add 100 c.c. of 
concentrated ammonia solution, with constant stirring, 
and evaporate to dryness on the steam-bath. What 
is formed? Recrystallize the product from hot 
water, and determine its melting-point, crystal form, 
solubility, color, taste, odor, etc. Does the substance 
dissolve more readily in ammonia solution than in 
water? Explain. Write out carefully all reactions, 
and explain each step. Save specimens of both sub- 
stances made, and calculate the yield in each case. 





EXPERIMENT 65. 
¢, erm . 


PHENYL CYANIDE (BENZONITRILE). 


Grind together intimately 40 grams of dry sodium 
benzene-sulphonate and 20 grams of potassium cya- 
nide, and distil the mixture from an iron or copper 
retort, the delivery-tube of which is connected with 
a receiver by means of a bent adapter. What sub- 
stance distils? Has it a bad odor (cf. Experiment 
30)? What remains in the retort? Proveit. Put 
half of the oil into a 500 c.c. flask, add 150 c.c. of 
strong caustic potash solution, connect the flask with 
a return-condenser, and boil the contents until the 
oil disappears. What is formed? What gas is 
given off? After cooling, acidify the solution with 
hydrochloric acid. Filter off the precipitate formed, 
and recrystallize it from -hot water. Determine its 
melting-point and properties. .What is it? Write 
out all reactions carefully, explaining each step, 
and save specimens of the two substances obtained. 


<tr 


Ez: 


Alerifion 





EXPERIMENT 66. 
PHENOL. 


Dissolve 40 grams of the dry sodium benzene- 
sulphonate in as small a quantity of hot water as 
possible in a silver, nickel, or iron crucible,! and add 
80 grams of solid caustic potash. Heat the crucible 
in an oil-bath or Meyer air-bath (see Lassar-Cohn, 
page 156), or with a direct flame, to 250°-276° C., for 
an hour, with constant stirring. The temperature 
is taken with a thermometer placed in a thin glass 
or copper tube closed at one end. When cold, dis- 
solve the melted mass in a small quantity of hot 
water, acidify with hydrochloric acid (what gas is 
given off?), and take up the oil, which separates, 
with ether. Separate the ether extract, dehydrate 
it with potassium carbonate in the usual way, put 
it into a distilling-flask, connected with a condenser 
and receiver, and evaporate off the ether. Then 
increase the heat and distil the oil, which should 
be afterwards cooled in a freezing mixture, and 
the crystals drained thoroughly on a Witt plate 
by suction. Determine odor, taste (poison), color, 
crystal form, boiling-point, solubility, ete. By what 
other method have you already made this substance ? 
Make a solution in water, and perform the following 


experiments : — 


1 Use an autoclav if available. See Gattermann, page 64. 





1. Add a few drops of ferric chloride solution. 

2. Add 4+ volume of ammonia solution, and then 
a few drops of a solution of bleaching-powder (1 part 
to 20 of water). 

3. Add a few drops of bromine water. 

Describe what takes place in each case, and write 
out all reactions. Save a specimen of the substance. 


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EXPERIMENT 67.? 


ORTHO AND PARANITROPHENOL. 
(Hoop. ) 


Mix 80 grams of nitric acid (sp. gr. 1.84) and 
120 grams of water in a }-liter flask. Cool the mix- 
ture with cold water, and add to it, gradually, and 
with constant shaking, 40 grams of melted phenol.? 
After the mixture has stood twelve hours, pour off 
the acid liquid from the brown oil formed, wash the 
oil once or twice with water to free it from acid, and 
subject the brown oil to distillation in steam. For 
this purpose generate the steam in a copper boiler 
and pass it into a round-bottomed copper or glass 
flask of about 8 liters’ capacity, containing the oil 
and water, and which is heated by means of a burner 
(see Lassar-Cohn, page 33) What passes over with 
the steam? Continue the distillation until the dis- 
tillate passes over almost colorless, and the residue 
in the distilling-flask no longer has the odor of the 
volatile oil. Filter off the solid in the receiver, drain, 
and recrystallize from alcohol. 

After the distilling-flask has cooled, filter off the 
crystals and extract the black resinous mass repeat- 
’ edly with boiling hot concentrated hydrochloric acid. 
Decant off the hydrochloric acid solution from the 
tarry mass, concentrate by evaporation, and allow to 


1 See Gattermann, page 267. 


* Do not allow phenol to come into contact with the skin. It pro- 
duces painful burns. 





cool. What are the crystals which separate? Re- 
crystallize them from the same solvent, if colored. 
Determine the crystal form, melting-point, solubility, 
volatility, color, odor, taste, etc., and yield of both 
substances. Have they acid properties? Explain. 
Write out all reactions, and save specimens of the 
two nitro-phenols. 


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* ue A 
ae 8 





EXPERIMENT 68, 


PICRIC ACID. 
(Hoop.) 


Heat together in a round-bottomed 4-liter flask to 
100° C. a mixture of 20 grams of phenol and 20 grams 
of concentrated sulphuric acid until complete solu- 
tion takes place! What is formed? Remove the 
burner, dilute with twice the volume of water, and 
add the solution (from a separating-funnel, and with 
constant shaking), gradually and carefully, to 100 
grams of nitric acid (sp. gr. 1.4). Warm the mix- 
ture on the water-bath until the red color changes to 
yellow, then pour into a liter of water, filter off the 
crystals on a Witt plate, drain thoroughly, wash with 
water, and purify by recrystallization from hot water 
containing .1% sulphuric acid. Saturate some of the 
crude picric acid with a solution of sodium carbonate, 
and add to the hot filtered solution a few crystals of 
sodium carbonate. What takes place? Explain. 
Determine color, odor, taste (poison), crystal form, 
melting-point, solubility, etc., of the acid. Does the | 
solution of the acid dye silk or wool? Does the dry 
sodium salt or the acid explode when heated or 
struck with a hammer? Save specimens of both the 
acid and the sodium salt, and write out all reactions. 


1 A sample taken out of the mass should be completely soluble 
in water. 





EXPERIMENTS 69 AND 70. 


BENZOIC ACID. 
(Hoop.) 


Boil 10 grams of benzyl chloride Gn a 500 c.c. 
retort with neck directed upwards), with a mixture 
of 30 grams of nitric acid (sp. gr. 1.31) and 20 grams 
of water until completely decomposed (about ten 
hours). When the odor of benzyl chloride has dis- 
appeared, and no oil separates out on cooling, let the 
contents of the retort cool, and filter off the crystals. 
If the crystals are colored, decolorize them by boiling 
the aqueous solution with boneblack, or by recrystal- 
lization from boiling dilute nitric acid. What is this 
substance thus obtained? By what other method 
have you already prepared it? Determine its melt- 
ing-point, odor, taste, crystal form, solubility, etc. 
Write out all reactions, and save a specimen of the 
acid. 





EXPERIMENT 71. 


Put a gram of benzoic acid in a 1-liter distilling- 
flask with 200 c.c. of water. Connect with a steam- 
boiler and with a condenser. Heat the distilling- 
flask and distil with steam until only 100 c.c. of 
water remain in the flask. Neutralize the distillate 
with ammonia solution, and evaporate to a small 
volume; acidify with dilute sulphuric acid. What 
takes place? Explain. Why was ammonia solution 
added ? | 


EXPERIMENT 72. 


Sublime a small quantity of benzoic acid by either 
of the methods given in the text-book, pages 323 and 
324. Or put some into the bulb of a straight cal- 
cium chloride tube, heat until the acid melts, and 
then pass a slow current of air through the tube. 
Increase the length of the tube if necessary by 
fastening a piece of paper, rolled to the same diame- 
ter as the tube, to it by a rubber band. Save 
a specimen of the sublimed substance. 





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EXPERIMENT. 73.1 
ETHYL BENZOATE 
1. 


(Hoop.) 


Dissolve 20 grams of benzoic acid in 80 grams of 
absolute alcohol, and pass a rapid current of dry 
hydrochloric acid gas through the cooled solution, 
until 4 grams of this gas have been absorbed. The 
hydrochloric acid gas is best generated by dropping 
from a separating-funnel concentrated sulphuric acid 
into a liter Erlenmeyer flask, half filled with concen- 
trated hydrochloric acid, and drying the gas by passing 
it through a wash-bottle containing sulphuric acid. 
When the solution has absorbed the 4 grams of 
hydrochloric acid gas, connect the flask with a return- 
condenser, and boil gently for four hours. Pour the 
contents of the flask into water, separate the oil from 
the water, wash with dilute sodium carbonate solution 
until the acid is removed, then with water. Sepa- 
rate as completely as possible from the water, dry 
with ignited potassium carbonate, decant from the 
carbonate, and distil. 

Determine boiling-point, color, specific gravity, 
odor, taste, solubility, etc., and yield of the sub- 
stance. What is formed when some of the substance 


1 The second method gives the better results. 


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is boiled with caustic potash solution? Try it. 
Write all reactions, and save a specimen of the 


ester. 


EXPERIMENT 73. 


ETHYL BENZOATE. 
2. 


Dissolve 25 grams of benzoic acid in 50 grams of 
absolute alcohol, add to the solution 5 grams of con- 
centrated sulphuric acid, and heat the mixture in a 
flask connected with a return-condenser for three 
hours. Pour the contents of the flask into five times — 
its volume of water, neutralize the acid with dry 
sodium carbonate, separate the oil from the solution, 
wash with water, dry with potassium carbonate, and 
distil. Then proceed as directed in Experiment 
73, 1. 





EXPERIMENT 74. 
PHTHALIC ACID. 
(Hoop. ) 


Grind together 25 grams of naphthalene and 100 
grams of good bleaching powder, and put the mix- 
ture into a 1-liter flask with 250-300 c.c. of water. 
Then add gradually concentrated hydrochloric acid, 
shaking the flask, till all the bleaching powder is 
decomposed. What is formed? Pour off the acid 
solution from the pasty mass, wash with lukewarm 
water once or twice, and drain thoroughly. Put the 
purified substance thus obtained into a tubulated 
retort with upright neck, and boil gently with ten 
times its weight of nitric acid (sp. gr. 1.45). The 
nitric acid should be added a little at a time, and, 
after heating awhile, more is to be added, and so on. 
When the oil has passed completely into solution 
distil off most of the nitric acid, and after changing 
the receiver, sublime the residue in a current of 
carbon dioxide. What passes over? Save a speci- 
men of this substance, and recrystallize the rest from 
water. Determine its melting-point, crystal form, 
color, taste, etc. Is it an acid? Save a specimen 
of the acid, and write out all reactions. 





EXPERIMENT 75. 
SALICYLIC ACID. 


Boil 5 c.c. of oil of wintergreen with 100 c.c. of 
a 20% solution of sodium hydroxide in a round- 
bottomed flask connected with a return-condenser 
until it has all disappeared. What is formed? When 
cool, acidify with hydrochloric acid. Filter off the 
precipitated substance, recrystallize it from water, 
and determine its melting-point, color, crystal form, 
taste, etc. What change takes place when some of 
the substance is carefully heated in a dry test-tube? 
What are the products? Prove it. Dissolve some . 
of the acid in water, and add a few drops of a solu- 
tion of ferric chloride. What takes place? Write 
out all reactions, and save a specimen of the acid. 





EXPERIMENT 76. 
SALICYLIC AND PAROXYBENZOIC ALDEHYDES. 


Dissolve 50 grams of phenol in a solution of 
sodium hydroxide (containing 100 grams of sodium 
hydroxide to 200 grams of water) in a 1-liter round- 
bottomed flask. Connect with a return-condenser, 
heat the flask in a water-bath until the temperature of 
the bath reaches 60°, and then add gradually through 
the inner tube of the condenser, with thorough shak- 
ing, 75 grams of chloroform. Complete the reaction 
by heating the contents of the flask to boiling for 
half an hour. Then distil off the unused chloro- 
form with steam. Acidify the contents of the flask 
with dilute sulphuric acid and again distil in steam. 
What distils with the water? When drops of oil 
cease to distil, extract the distillate with ether once 
or twice, and shake the concentrated ethereal solution 
in a separating funnel with a saturated solution of 
sodium acid sulphite.2 What takes place? Explain. 
Draw off the lower layer, filter, and shake the 
filtrate again with the ethereal solution, and again 
filter. Continue this process as long as crystals 
form. Wash the crystals on a Witt plate with 
alcohol, drain completely by suction, and decom- 


1 See Gattermann, page 312. 

* The sodium bisulphite solution should be freshly made, and is 
best prepared by placing powdered sodium carbonate in a flask, 
covering it with a layer of water and saturating with sulphur 
dioxide. The commercial sodium, bisulphite will not answer for 
the purpose. 








» 
if 
ms 


pose them by warming with an excess of dilute sul- 
phuric acid. When cold, take up the oil resulting 
with ether, dehydrate the ethereal solution with 
calcium chloride, put into a distilling-flask, evap- 
orate off the ether, and finally increase the heat, and 
distil the substance. Determine odor, color, boiling- 
point, specific gravity, solubility, volatility, etc., of 
the substance, and save specimens of it and its 
sodium bisulphite compound. 

Filter the contents of the flask Crom which the 
oil was distilled), while hot, through a wet filter, 
and extract the cold filtrate with ether. Separate 
the ether from the aqueous solution, evaporate off 
the ether, and recrystallize the product from hot 
water. What is it? Determine color, crystal form, 
melting-point, solubility, volatility, etc. Show how 
you could distinguish between the two aldehydes by 
the reaction with ferric chloride. Save a specimen 
of the substance, and write out all reactions. 





EXPERIMENT 77. 
ROSANILINE. 


Heat 1 gram of a mixture of aniline and para- 
toluidine (2 molecules of aniline and 1 of paratolui- 
dine) in a test-tube or small flask in an oil or sul- 
phuric acid bath (Hood) for one and a half hours to 
180°-200° C., together with 3 grams of mercuric chlo- 
ride and 2 grams of aniline. What is formed? Ex- 
tract the melted mass with alcohol, filter, and 
evaporate to dryness on the water-bath. Does the 
aqueous solution of the substance dye wool, silk, or 
cotton? ‘Try it. Save a specimen of the colored 
solution, and write out the reaction. 


EXPERIMENT 78. 


Dissolve 2 or 3 grams of picric acid in hot water 
containing a small amount of sulphuric acid. Steep 
in this hot solution a piece of white yarn or flannel 
and a piece of white silk. Press out the excess of 
solution, and dry; then do the same thing with a 
piece of white cotton or linen cloth, and dry. Deter- 
mine which of the materials are dyed permanently 
by washing them all in hot water and drying. 
Explain. Save samples of the dyed material. 





EXPERIMENT 79. 
INDIGO-WHITE. | 


1. 


Dissolve some stannous chloride (tin salts) in 
alcohol, and add enough of an alcoholic caustic soda 
solution to dissolve the stannous acid precipitated, 
and then a slight excess of the alkali. Add this 
solution to some powdered indigo in a flask, and 
warm the solution gently. Decant the clear soiu- 
tion, and pass a current of air through it, or expose 
it to the air in a shallow dish. What takes place? 
Explain the whole process. 





EXPERIMENT 79. 
INDIGO-WHITE. 
2. 


Dissolve one gram of indigo carmine in 250 c.c. of 
water contained in a 500 c.c. flask and add to this 
solution one gram of sodium hydrosulphite. Shake 
the mixture thoroughly until the indigo carmine is 
completely reduced and a yellow solution results. 
What has taken place? Explain. What is indigo car- 
mine? What is sodium hydrosulphite? Saturate some 
pieces of cheese cloth with the indigo-white solution, 
dry in the air and then wash with water. Is the cloth 
permanently dyed? Expose some of the solution to 
the air in a shallow dish or blow air through some of 
the solution and note what happens. Explain. 








EXPERIMENT 80. 
ANTHRAQUINONE 
1 


Dissolve 10 grams of pure anthracene in the neces- 
sary quantity of boiling glacial acetic acid, contained 
in a round-bottomed flask connected with a return- 
condenser. Filter the solution if necessary. Add 
gradually and in small portions, through the inner 
tube of the condenser, keeping the solution boiling, 17 
grams of chromic acid dissolved in glacial acetic acid. 
Continue the heating until the solution becomes in- 
tensely green colored, then distil off the greater part 
of the glacial acetic acid and save it. Pour the resi- 
due into water. What is precipitated? After allow- 
ing to stand for awhile, filter, wash with water, hot 
dilute caustic soda solution, and finally with hot 
water. Recrystallize from hot glacial acetic acid 
or benzene. Determine color, crystal form, melting- 
point, solubility, etc., of the substance. Does it sub- 
lime? Warm one part of the substance with zinc- 
dust (2 parts) and caustic soda solution (80 parts 
of 50% solution). What takes place? Explain. 
Save a specimen of the anthraquinone, and write out 
all reactions. 





EXPERIMENT 80. 


ANTHRAQUINONE. 
as 


Cover 5 grams of anthracene with six to eight 
times its weight of alcohol (so that on boiling the 
alcohol only part of the anthracene dissolves), then 
pass a strong current of chlorine into the boiling 
liquid. After some time a solution is obtained, 
which on further addition of chlorine gives a pre- 
cipitate (?). After cooling, filter, wash the precipi- 
tate with cold alcohol, then with dilute caustic soda 
solution, dry, and sublime. Then proceed as directed 
in Experiment 80, 1. 


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EXPERIMENT 81.! 


ALIZARIN. 
(Hoop. ) 


Heat 20 grams of anthraquinone* with 60 grams 
of concentrated sulphuric acid to 250°—260°, until, on 
taking out a small quantity and adding it to water, 
no anthraquinone is precipitated. What is formed? 
Pour the mixture cautiously into a large quantity 
of water contained in a porcelain dish, stirring the 
water vigorously. Warm, and neutralize, while hot, 
with chalk or slaked lime; filter the boiling hot 
solution through muslin or by the method of reverse 
filtration. Evaporate to about half the volume, filter- — 
ing if necessary. Then add a saturated solution of 
sodium carbonate until all the calcium has been 
precipitated. Filter the boiling hot solution and 
evaporate, first over a free flame and then to dryness 
on the water or steam bath. Save a specimen of the 
crystallized sodium salt, and convert the rest into 
alizarin. For this purpose dissolve one part of the 
sodium salt in as small a quantity of hot water as 
possible in an autoclav, add 5 parts of solid caustic 
soda and 0.3 parts of potassium chlorate. Heat the 
mixture for 20 hours to 170°. Let cool, and remove 
the melted mass by boiling with water and by mechan- 
ical means. Saturate the solution thus obtained with 
dilute sulphuric acid, boil for fifteen minutes, filter 
1 See Gattermann, page 333. 2 Use a 1-liter flask with long neck. 





while hot, and wash the precipitate with hot water 
until the sulphuric acid is removed. Dry and sublime. 
What is this substance? Determine its color, melting- 
point, crystal form, solubility, volatility, ete. Does 
it dissolve in alkalies? Explain. What is formed by 
heating some with ten times its weight of zinc-dust 
in a test-tube? Save a specimen of the alizarin, and 
write out all reactions. 





INDEX 


EXPERIMENT 
Acetic acid : . : : . ' 4 : A a Bt 
Acetic acid, detection . ; , ‘ ‘ : . one 
Acetic aldehyde : ‘ . . : : ‘ ee Oo Fee 
Acetic ether ; : ‘ ; : : * ; eee 
Acetic ether, eaverincaaen ‘ : . ° Fi eee 
Acetyl chloride ; : - . ae : or 2D Sa 
Acetylene . ee ats : : : : ; s i . 68 
Acrolein . : ; A . 4 ; ; 4 A - oe 


Alcohol, absolute . : ; : : ‘ : ‘ eae 
Aldehyde . ‘ ; A : ; 4 ; : «Sa Ae 
Aldehyde ammonia . : : ‘ : ‘ : . (14 


Aldehyde, detection . : ; : : : ; : . ohh 
Aldehyde, Wate ; : p ; A : : . o2 
Alizarin . : ‘ ‘ - . ee ee : 2 
Aluminum acetate . : ; : : : ; : se 
Amine, primary, detection ; ; . ‘ : ; mae | 
Ammonium cyanate, urea from ‘ : : ° . 47, 48 
Ammonium sulphocyanate : : : ‘ : x ae 
Aniline. : - ; : ; : A : : Fae 6 
Aniline, detection . : ‘ ; ‘ ; ce 4 « . 61 
Anthraquinone . : 6 ‘ ; ‘ . ; ; aU 
Benzene . ‘ - : = : <. 58 
Benzene and eoinane separation ; : ¥ : : . 56 
Benzene-diazonium chloride . ‘ ‘ . : a . 62 
Benzene-sulphon-amide . ' : ; ; 5 . . 64 
Benzene-sulphon-chloride : ; . F ‘ . . 64 
Benzene-sulphonic-acid . ; <<: ee “ ° : <= Oe 
Benzoic acid. i" ; 5 3 ° = : 69-72 
Benzoic acid, benzene num : : . . 4 : . 55 
Benzoic ether . ; ; . A : 2 , a o ule 
Benzonitrile . ~ . . “ ° : : ° . 65 


Benzyl chloride : ° : : . - .- OR It 
Bromine, detection . ‘ . ° ° ° F . . 43 





Calcium carbide 

Calcium ethyl sulphate 
Cane sugar, hydrolysis 
Carbamine, phenyl 
Carbolic acid 

Cellulose 

Chloroform : 
Cyanate, potassium . : 
Cyanbenzene 3 
Cyanide, potassium . “ 


Diazo compounds ; 
Diethyl oxalate : . 
Dinitrobenzene 
Distillation, fractional 


Ether : ° 
Ether, acetic 
Ethyl] acetate 
Ethyl acetate, saponification 
Ethyl aldehyde 
Ethyl benzoate . 
Ethyl bromide . 
Ethyl ether 
Ethyl formate . 
Ethylene . 
Ethylene bromide 


Fehling’s solution 
Fermentation of glucose 
Ferric succinate, basic 
Ferricyanide, potassium 
Flashing-point of kerosene 
Formic acid ~ . . 
Fractional distillation . 


Glucose, fermentation 
Glucose, reducing action . 
Glycerol . : . ° 


Hydrolysis of cane sugar . 


Indigo-white . : . 
Iodine, detection “ 


EXPERIMENT 


13, 


53 





‘ 


Iodo-benzene . ace  e 
‘Iodoform . x : : 
Iron acetate ; ‘ 


Isocyanide, phenyl . ° 
Kerosene, flashing-point . 


Marsh gas 


Melting-points, dutenainnan : 


Metaldehyde . : 4 
Methane . 


Naphthalene, oxidation to phthalic acid 


Nitrobenzene 


Nitrophenol, ortho- and para- 3 


Oil of wintergreen, saponification 


Orthonitrophenol 

Oxalic acid 

Oxainide ? 
Oxybenzoic aldehydes . 


Palmitic acid . ; ° 
Paraldehyde . ; . 
Paranitrophenol 


Paroxy benzoic aldehyde 
Phenol A 
Phenyl eyanider 

Phenyl iodide . : 4 
Phenyl isocyanide 
Phthalic acid 

Picric acid ; ° 
Picric acid, dyeing sf 
Potassium cyanate 
Potassium cyanide . : 
Potassium ferricyanide 
Potassium sulphocyanate . 


Rosaniline : 


Saccharose, hydrolysis 
Salicylic acid 

Salicylic aldehyde 
Saponification . 


EXPERIMENT 


. pate 
oes ap 
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ee 

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74 
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Schweizer’s reagent . ; 7 . 
Silver carbide . 5 . 
Soap. 

Sodium Beonene eal phonete 

Starch ; ‘ : “ 


Starch, A tention . : 
Starch, hydrolysis . : : 
Stearic acid 

Sulphocyanate, ammonium 
Sulphocyanate, potassium 
Sulphuric ether 


Toluene, separation from benzene 
Trinitrophenol . 


Urea, detection 
Urea, from ammonium cyanste 


Urea, from urine : : : . 


Willesden process of waterproofing . 


EXPERIMENT 


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Whiting’s Physical Measurement. I. Density, Heat, Light. and Sound. IT. 
Magnetism, Electricity. ILI. Principles and Methods of Physical Measurement, 
cal Laws and Principles, and Tables. Parts I-IV, in one volume, $3.75. 


Whiting’s Mathematical and Physical Tables. Paper. socents. ae oy ce Hs ‘age. 
Williams’s Modern Petrography. Paper. 25 cents. ee, 
















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For elementary works see our listof- iy: 
books in Elementary Science. a. eae 


D.C. HEATH & CO., Publishers, eee New York, Crago 


